title: Preparation of anti-vicinal amino alcohols: asymmetric synthesis of D-erythro-sphinganine, (+)-spisulosine, and D-ribo-phytosphingosine.
abstract: Two variations of the Overman rearrangement have been developed for the highly selective synthesis of anti-vicinal amino alcohol natural products. A MOM ether-directed palladium(II)-catalyzed rearrangement of an allylic trichloroacetimidate was used as the key step for the preparation of the protein kinase C inhibitor D-erythro-sphinganine and the antitumor agent (+)-spisulosine, whereas the Overman rearrangement of chiral allylic trichloroacetimidates generated by the asymmetric reduction of an α,β-unsaturated methyl ketone allowed rapid access both to D-ribo-phytosphingosine and L-arabino-phytosphingosine.
authors.affiliation: WestCHEM, School of Chemistry, The Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, United Kingdom.
authors.forename: Ewen D D
authors.initials: ED
authors.lastname: Calder
authors.forename: Ahmed M
authors.initials: AM
authors.lastname: Zaed
authors.forename: Andrew
authors.initials: A
authors.lastname: Sutherland
mesh_terms: D008055:Lipids / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013110:Sphingosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C521790:D-ribo-phytosphingosine; D008055:Lipids; D013110:Sphingosine; C408363:spisulosine